Loudon Chapter 7 Review: Cyclic Compounds

CHEM 3311, Jacquie Richardson, Spring 2010 - Page 1

The most common cyclic compounds well see are derivatives of cyclohexane,
because six-membered rings are the most stable. Although cyclohexane is often shown in
a top-down view, thats not how it exists in space its puckered into a chair-like shape,
which is called chair cyclohexane.

View from above View from the side

We can learn a lot about the behavior of this molecule by looking at the geometry of the
chair. A lot of the time its easiest to draw the template for chair cyclohexane, and then
fill in the details for whatever specific molecule were interested in. Every atom around
the ring has two other things attached to it. It turns out that one of these is equatorial
(because it lies near the equator of the molecule) and one is axial (because its pointing
up or down along the axis).
The drawing is made of four sets of parallel lines. First, draw the ring, and then
fill in the equatorial lines, which are all parallel to some part of the ring.

all equatorial bonds

Note that every ring carbon thats pointing upwards has an equatorial bond going down,
and vice versa. Now you can fill in the axial bonds, which are all vertical.

all axial bonds all equatorial bonds all total bonds

Note that every ring carbon thats pointing upwards has an axial bond thats also going
up. One other characteristic of this molecule, though, is that it can flip between two states.
Ive labeled one particular carbon with an asterisk; you can see that during this flip it
goes from pointing up to pointing downwards. Based on what we just saw, this means
that its upwards-pointing bond and its downwards-pointing bond toggle which one of
them is axial and which one equatorial.

down is axial, ring flip down is equatorial,

up is equatorial * up is axial
*
Now we can fill in the details for whatever molecule we want, but there are a few
rules to follow:
Anything thats shown with a bold bond in the top-down view is up or
slightly up in the chair view.
Anything thats shown with a dashed bond in the top-down view is down
or slightly down in the chair view.
 Loudon Chapter 7 Review: Cyclic Compounds
CHEM 3311, Jacquie Richardson, Spring 2010 - Page 2

Anything thats straight up or down is axial.

Anything thats slightly up or slightly down is equatorial.
Cis and trans refer only to the comparison between bold and dashed. If
both groups youre comparing are bold or both are dashed, theyre cis to
each other. If you have one bold and one dashed, theyre trans. Axial and
equatorial dont matter at all here.
Doing a ring flip converts anything equatorial to an axial position, and
vice-versa, but it doesnt change whats bold or dashed. If a group is up,
then it should always be up (unless youre flipping the entire object
upside-down).
With this is mind, lets work through an example. You can label one of the carbons in the
top-down view, and arbitrarily put the same label on any of the carbons in the chair view.
I like choosing my label positions so the groups are all in front where I can see them, but
any place is fine. Then you can fill in the groups. CH3 is on the starred carbon and bold,
so I put it there coming upwards. Cl is on the first carbon moving clockwise from the
starred carbon and its dashed, so I put it there pointing down. This is true for both chair
forms of the molecule.
CH3
Cl OCH3 CH3
*
ring flip
= CH3 H3CO *
Cl*
OCH3 Cl
No matter what, the CH3 and the OCH3 are always up or slightly up, and the Cl is always
down or slightly down. The ring flip just swaps axial for equatorial.
Where is can get a bit confusing is in the fact that a lot of the time, people prefer
to show just a single type of chair: either the leftmost carbon of the ring is always
pointing up for them, or its always pointing down. To achieve this, they combine a ring
flip with a simultaneous rotation of the ring by 1/6 of a turn.

ring flip rotate by 1/6 turn

*
* *
After this rotation, the starred carbon still has up as axial and down as equatorial, its just
moved around the ring a bit so that its no longer the rightmost carbon. We can apply this
to our example:
CH3
Cl OCH3 CH3
H3CO CH3
* ring flip rotate by
= CH3 H3CO * 1/6 turn
*
Cl* Cl
Cl
OCH3
 Loudon Chapter 7 Review: Cyclic Compounds
CHEM 3311, Jacquie Richardson, Spring 2010 - Page 3

This shows how to draw both forms, but it doesnt tell us anything about which form is
most favored. It turns out that almost every group prefers being equatorial to being axial.
If a group is axial, it experiences 1,3-diaxial strain from bumping against the two other
groups that are axial and pointing in the same direction.

H CH3
OCH3 H H
H
H3CO * = 1,3 diaxial strain interaction
CH3 H
Cl* H Cl
Each group has a set cost for being axial, but generally if youre comparing the two forms
of a molecule, you can just count how many groups are where. For the left form in the
above picture, theres only one group axial. For the right form, there are two groups axial.
So the left form would be the most stable.
Why does this preference exist? You can explain it using Newman projections
from before. Again, we choose a bond to sight along, but the ring is made up of parallel
lines. So were actually sighting along two bonds simultaneously. We can do this along
either of the two bonds attached to the carbon that has the group of interest on it. When
we do, it becomes apparent that the biggest difference between being axial or equatorial
is gauche interactions. Being axial means that a group has two more gauche interactions
than it otherwise would, with part of the ring itself. Which part of the ring appears gauche
depends on which two bonds you sight along, but in reality both parts are gauche all the
time that the group is axial.
gauche
OCH3 H
OCH3 H CH3
H
H
H H
H CH3 H H
Cl H Cl H
H H

gauche
OCH3 H OCH3 H
H CH3
H
H H
H CH3
Cl H Cl
H H
H H
 Loudon Chapter 7 Review: Cyclic Compounds
CHEM 3311, Jacquie Richardson, Spring 2010 - Page 4

One more topic thats covered in this chapter is the stereochemistry of

additions. This is a return to the material covered in chapter 5, but now were looking at it
from a perspective of stereochemistry. When we add two groups to an alkene, there are
three different possibilities for stereochemical outcomes.
Syn addition: both groups always add to the same face. The key here is
that both groups are added at the same time, from the same direction in
other words, this is a concerted mechanism. Reactions in this category are
hydrogenation and hydroboration-oxidation (hydroboration is the step that
determines stereochemistry; the oxidation swaps the B for an OH without
changing the direction it points).
Anti addition: the groups add to opposite faces. A common factor among
the mechanisms weve seen is a three-membered ring that gets popped
open, but this wont always be the case. Reactions in this category include
halogenations, halohydrin formation, and oxymercuration (but not
reduction thats a separate deal, since the mercury gets replaced with an
H that could be pointing either direction at random).
Random addition: sometimes they add to the same face and sometimes
they add to opposite faces. This category includes anything that goes by a
carbocation or carbon radical mechanism, since both these carbons go sp2
and lose all their stereochemical information. Reactions in this category
include acid-catalyzed hydration and HX addition with or without radical
initiators
H H
1) BH3
2)H2O, OH-, Syn addition
H2 O 2 OH OH

Br Br
Br2
Anti addition
Br Br

H H
Br2, ROOR

Br Br
Random addition
H H

Br Br

One last thing to point out: anti addition is not the same thing as anti-Markovnikov!
Hydroboration is an anti-Markovnikov-style addition, but its not an anti addition.